Aromatic recovery process



Jan. 4, 1955 1. F. TEYKI. :TAL

ARoMATIc RECOVERY PRocEss Filed 'OG 7, 1952 Y wm INVENTORS /rw'n F. Teyk/ James 5. Part rsan 2,69sgss1rf'ff ARQMATIC RECOVERY; PROCESS Irvin aF. .'=I`eykl, .I-Ioiiston,..and,JamesiS.Y Patterson, rTexas City, TeX., .assignors,. by mesneassignmentsyto Pall z American .Reiniiigorporatiom..1Ifexas City,l Tex., a corporatonof. r[Feiras ..1

Thisfinvention..relatesfto the vpurification-'ofV a solvent employed in an extractive distillationzproeess'to recover a. pure Aaromatic from a narrowboiling` hydrocarbon frac# tion.4 VMore particularlydt concerns the lremoval of a troublesome sludge whichfaccumulates in a .-phenolicsolventernployedvin such aprocess. 5

To :recover pure.aromatic-hydrocarbons from petro-` leum distillates and the like, it is first necessary to fractionally, distill the sameoto f concentrate-.the aromatic.

Aromatic compounds .-in admiXture-with closely boiling hydrocarbonscannot ordinarily be recovered in .-high purity by Vdistillation-alone because of the--existenceof azeotropicmixtures tof` thearomaticsand other hydrocarbons.: It is, therefore, .common practicelo extractivelydistill. very., narrow boiling, aromatic-containing concentrateswith a suitable solvent *.It has been .found thata ,troublesomefsludgeis formedrduring'such al process, whiclni allowed `to accumulatefin theffsolvent-:to more-- than. a certain .maximum concentration it-willsettleout..

on..thelbubbley cap trays.. of` thecextractivetdistillation tower... .Operation of the tower becomeserratic whenza quantity of this sludgehas accumulated -on -the trays and-vincipient flooding often occurs. iron derivatives t and in the :case .of phenolic solvents,

These sludges comprise which. are preferablyemployedga substantialainount of aryl lethers. s

It is an obiectnof tliepresent.inventiorntoprovide a methodaof reducingtheasludge,content of rthefsolvent,Y

employedv in an raromatic :recoveryr-eittractive ,distilla tion process.A VA further. object is to leliminate incipient flooding and other :operationaLtailures:in theextractive otherobject isv to maintain thesolventat its highest etli, ciency. These and additional, objectstwill become apparent from the Vfollowing ldetailed description of the present invention.

Briey, it has ybeen discoveredlthat the 'sludgecontent of the circulating solvent employed-t separate a pure ,.45 distillation tower. employedfin such a .process.. f Still: an-.,

aromatiofrom ahydrocarbon distillate "by vaporphase Y extraction or extractive distillation',vv can* be maintained below a certain'A .maximumi'concentration (hereinafter moreV fully zdeiined') by 'withdrawingca relatively 'small" portioiifof the .rich solventfleaving f the :extractive distilla` tion towerandontaotingfitwith additionaliaromatic andl water; f- The. rich solvent,` waten and.4 addedfaromaticare f vigorously agitated; andihen settledw A two-or three-l phasesystern..tlienforins,` of whiclrthe lower phase or phases ,comprise water anda substantial amount of the.v

ludge introduced to thefmixer. Theupper phase cornprising substantially all of the Aaromatic and .solvent is' then' recycled to the solvent reactivator wherein the solventisrecovered'from-'the aromaticg water, etc. and-then recycled to the extractionzone.`

ln thedrawinglis shown a simpliedscheinatic Vliow diagram of. the equipmentgforcarrying out this invention. Referrina to thefdrawirig,l a e:-isolin'ef;distillate fraction,

e.- g. such as resultsv rfioninhydroforining a naphthenic` heavy naohtha in accordance, with theprocesa-set fort-lr in U. S. 2,388,336, containinga relatively smallamount of benzene ist-introduced to precisioir'ractionation tower-10 via ylinell. The distillate istherein-fractionated to re' move overhead those materials lighterfthan benzene. Benzene. and other. closely boiling materials..are.:withdrawn w from.towerf.1l via line 12 and introduced.. tov a second precisionfractionation.tower 2.3 whereinsubstantially .all .l

of the benzene is removed overhead via .line'14. The narrow.. boiling, benzeneLcontainingfraction is then. i11- 2,698,831 Patented Jan. 4, 1955 ICC troduced. to extractivedistillation tower .15.1 The rmaterialv heavier than. benzene, is withdrawn from tower-13 via line16.- .Bycarefully adjustingthe conditions .in towersll() and 13, the'overhead. fraction fromtower 13 which is introduced to extractive distillationfiower 15 e willeoritain at least about. 5 .to 10%,benzene.

The overhead fraction from tower 13, which may herel inafter be referred to as the.benzene.concentrate, is introduced to tower 15 Vvia line 14 at a temperature abovethe, boiling point of ,benzene and. contacted therein .with

phenol introducedto thetower 'via line 17. V.ThesolvenbK flows downward counter-current to theiup-owing vapors thereby selectivelyremoving the benzene from the closely boiling liydrocarbons.- These' closely-- boiling. hydrocar bons from which the benzene has been scrubbed pass out the top of tower-15 via line18. lThe rich'solvent containing the benzene is withdrawn from Ythetower via line 19 and is introduced to reactivatortower 20 (a distillal tion column) vwhereinthe benzene is stripped from the solvent which is. recycled to tower 15.via .line.17. The.

pure ,benzene passes out the top of tower'20 and is separated from water in condenserlland then. passed to storage, -not shown.

A portion of the rich solvent leaving tower 1S may be withdrawn from line 19 andintroduced via line 22,'``

through cooler 23 to mixer 24 wherein it is .admixed with pure benzene via line 25 and. water from line 26 in amounts hereinafter more fully defined. After agitation in mixer 24 the mixture is passed to settler 27 via line 28 where phase separation occurs and a lower aqueous layer is withdrawn via line 29. "The upper benzene-solvent l layeris deeanted via line 30 'and recycled to tower 20. The lower aqueous phase contains aV substantial portion of the sludge.:

The present invention particularly concerns the .re-

duction of the `solvent sludge contentandit should be un-A derstood that the fractionation and extractive distillation techniquesdescribed constitute known practice and .that no claim of novelty .is made thereto. A more detailed descriptionof a process, of this general typcvwhereby pure aromatics may be recovered is set forth ini U. S. Reissue Patent 22,379. The present invention constitutes an improvement in that and other such processes `wherein the problem of sludge formation has .been found to occur.

As noted above, the sludge comprises essentially aryl v ethers and .certainron compounds when. operatingvwith phenolic solvents. that the quantity of aryl` ether in the-circulating solvent should lbe maintained below about 8% and preferably below about.7% by weight of the'lean solvent to prevent sludge fromsettlingout on the bubble cap plates. wise,".the iron. content, based Aupon FegOa, should be below about L0.05% and preferably below-about 0.03% by weightof total. solvent to assure substantial freedom from sedimentation. The sludge, which is soluble `to some 4vextent in phenol, is preferentially. .water solubleA With such solvents 'it has been found Likewhen allowed to settle in such an aqueous mixture of l phenol andaromatic. It is evidentthat the constituents of the sludge vary in solubility over a. relatively wide range-and Ythat some are more oil soluble than others inasmuch as the removal of sludge in anygiven settling operation, in accordance herewith, 1s not complete.

About halt` of the sludge which enters thelsettler along with, the watenphenol and aromatic is ordinarily removed in each settling step. The aryl ether and iron contents, if initially above the critical concentrations, are thus `reduced to a satisfactory levelV in a relatively short time' and thereafter maintained g' in such condition. Whereas both maior sludae comnonentsrviz. aryl ethers and iron` should be maintained below the above figures and while reduction of one will accompany-reduction of the other, it is criticallv important that the aryl ether contentbe maintained therebelow. If vthe ether'content is maintained below such figure the riron content may rise somewhat above thestated maximum `without incurring sedimentation, etc. t

,An example of theoperation of the solvent purification technique is as fo'l10ws:.About`304 pounds'of rich solvent were removed fromA the base-of' the extractive distillation tower in one'hour andintroduce'd to themixer.' Thisistream analyzed 254'pounds of phenol, 33.5 poundsl of benzene, 16 pounds of sludge and contained 0.095 pounds of iron based on FezOs. A total of about 95.5 pounds of water and about 361 pounds of substantially pure benzene were mixed therewith and the mixture was settled. A three phase system formed, of which the top layer comprised about 295 pounds of benzene, 251 pounds of phenol, 9.4 pounds of sludge, 26.8 pounds of water and had an iron content of 0.065 pounds. The middle layer comprised substantially all water (about 68 pounds) and the lower layer comprised about 7 pounds of sludge, 3 pounds of phenol and contained about 0.036 pounds of iron. The top layer was recycled to the solvent reactivator tower wherein the solvent and benzene were separated and about 27 pounds of water were condensed from the benzene overhead. The lower layers in the settler were discarded. The reduction in sludge and iron (on the basis of FezOx) resulting from this single equilibrium treatment was, therefore. 43% and 38% respectively.

The purification of the phenol solvent in accordance herewith should be conducted at relatively low temperatures and preferably at a temperature below about 110 F. lt is, therefore. preferable to reduce the temperature of the benzene and the rich phenol leaving the extraction zone to at least this temperature prior to introducing same to the mixer. The temperature at which sludge may be removed from solvents other than phenol will vary in accordance with the solubility characteristics of the solvent relative to water and the aromatic hydrocarbon..

Thus, in the case of phenol, use of a temperature higher than about 110 F. results in substantial loss of solvent because of its increased solubility in water at higher temperatures. Similarly, the temperature-solubility relationship of water and solvents other than phenol. which may be used in place thereof, should be carefully observed in order to prevent such a loss of solvent.

The amount of the circulating solvent subiected to purification may vary with the amount of sludge present and the rate of its build-up. The amount and rate of build-up of sludge are in turn dependent upon a variety of factors, e. g. diolefin and oxygen content of the aromatic concentrate. temperature of the circulating solvent, and its velocity through the lines. etc. Generally, however, between about 10% and about 30% of the total volume of circulating solvent should be treated per day in accordance herewith to maintain the sludge within satisfactory limits. Greater amounts may be treated but it is usually economically uniustifiable.

It should be clearly understood, in connection with the volume ot' solvent treated. that in a system having, for

example, about 100 barrels of circulating solvent that far less than 10 to 30% of that total is treated in any single purification. In other words, while there are only 100 barrels of solvent in the system, the volume of solvent which passes any point in that system in a single day is many times greater than 100 barrels because of re-circulation. The amount of solvent withdrawn from a given stream for treatment in a single desludging operation is accordingly very much less than 10 to 30% of the total solvent passing that point. Thus, only a small portion, e. g. 0.25% to 1% of the total rich solvent leaving the extraction zone in one day need ordinarily be treated according to the present invention. Since from 10% to about 30% of the total solvent in the system is thereby treated in a days time, however, the proper balance is readily maintained.

The purification technique may be employed continuallv or only as needed to offset a rise in sludge content. Thus, it need not be operated every day if the sludge buildup is slight. The desludging process may operate intermittently on a batch basis or a substantially continuous process in which two or more settlers are alternately settled and filled may be employed.

The ratio of aromatic to solvent in the solvent purification step should be at least about 1:1, on a weight basis, and preferably about 1.5 :1. Greater quantities of aromatic offer no particular improvement but may be employed. It is preferred, as described, to treat the rich aromatic containing solvent to remove the sludge because the aromatic already present therein aids the complete admixture of the added aromatic and also because the temperature of the stream leaving the extraction zone is ordinarily lower and requires less cooling than the stripped solvent leaving the reactivator. It should be understood, however, that the lean solvent from the reactivator may be treated in a similar manner in accordance herewith.

The amount of water added to the rich solvent, and aromatic, should be at least about 10% by weight of the total mixture and preferably from about 15% to about 25%. More may be used but without added advantage.

Whereas the invention has been described with particular reference to the recovery of benzene and purification of a solvent comprising phenol it should be understood that it is not so limited and that various other solvents may be used; and depending upon the boiling range of the concentrate introduced to the extraction distillation tower various aromatics may be recovered and employed in accordance herewith. Thus, as examples of solvents suitable for the recovery of aromatics from such narrow boiling concentrates, are cresylic acids, alkyl phenols, aniline, diphenylamine, Carbitos, etc. The solvents must be chemically and thermally stable under the conditions encountered.

Aromatics such as toluene, xylenes and ethylbenzene, paracymene, naphthalene, methyl naphthalenes and the like may be recovered in pure form by proper selection of the solvent and employed in the solvent purification steps herein described similarly to benzene.

Having thus described the invention, what we claim as novel and desire to protect by Letters Patent is as follows:

l. in the process which embodies recovering a substantially pure aromatic from a vaporized narrow boiling hydrocarbon mixture by extraction with a liquid phenolic solvent, the improvement which comprises reducing the sludge content of said solvent by admixing at least a portion of the circulating solvent with at least about an equal weight of the substantially pure aromatic recovered in said process and a substantial amount of water at a temperature below that at which the solvent is substantially soluble in water, settling the aqueous mixture thus produced at such a temperature to obtain stratification thereof, recycling the upper solvent and aromatic-containing stratum to a solvent recovery zone and discarding the material below said upper stratum.

2. Tn the process which embodies recovering a substantially pure aromatic from a vaporized narrow boiling hydrocarbon mixture by extraction with a liquid phenolic solvent the improvement which comprises reducing the sludge content of said solvent by admixing at least a portion of the rich aromatic-containing solvent from the extraction zone with at least about an equal weight of the substantially pure aromatic recovered in said process and a substantial amount of water at a temperature below that at which the solvent is substantially soluble in water, settling the aqueous mix- .ture thus produced at such a temperature to obtain stratification thereof, recycling the upper solvent and aromatic-containing stratum to a solvent recovery zone and discarding the material below said upper stratum.

3. In the process which embodies recovering a substantially pure aromatic from a vaporized narrow boiling hydrocarbon mixture by extraction with a liquid phenolic solvent, the improvement which comprises admixing at least a portion of the rich aromatic-containing solvent with at least about an equal weight of the substantially pure aromatic recovered in said process and a substantial amount of water at a temperature below about F., settling the aqueous mixture thus produced at such temperature to obtain stratification, recycling the upper phenol and aromatic-containing stratum to a solvent recovery zone and discarding the material below said upper stratum.

4. The process of claim 2 wherein the narrow boiling hydrocarbon mixture comprises a benzene concentrate recovered from the gasoline fraction resulting from hydro-forming naphthenic heavy naphtha and the substantially pure aromatic is benzene.

5. In the process which embodies recovering substantially pure benzene from a narrow boiling hydrocarbon fraction by extractive distillation with a liquid phenolic solvent, the improvement which comprises admixing at least a portion of the circulating phenolic solvent with at least about an equal weight of substantially pure benzene and an amount of water equal to at least about 10% by weight of the total admixture at a temperature below about 110 F., settling the aqueous mixture thus produced at such a temperature to obtzinb stratif- References Cited in the le of this patent cation thereof, recycling the upper solvent an enzenecontaining stratum to a solvent recovery zone and dis- UNITED STATES PATENTS carding the material below said upper stratum. 2,375,035 Pierotti May 1, 1945 6. The improved process of claim 5 wherein the sol- 5 2,426,705 Patterson et al. Sept. 2, 1947 vent comprises essentially phenol. 2,523,554 Boatright et al. Sept. 26, 1950 

1. IN THE PROCESS WHICH EMBODIES RECOVERING A SUBSTANTIALLY PURE AROMATIC FROM A VAPORIZED NARROW BOILING HYDROCARBON MIXTURE BY EXTRACTION WITH A LIQUID PHENOLIC SOLVENT, THE IMPROVEMENT WHICH COMPRISES REDUCING THE SLUDGE CONTENT OF SAID SOLVENT BY ADMIXING AT LEAST A PORTION OF THE CIRCULATING SOLVENT WITH AT LEAST ABOUT AN EQUAL WEIGHT OF THE SUBSTANTIALLY PURE AROMATIC RECOVERED IN SAID PROCESS AND A SUBSTANTIAL AMOUNT OF WATER AT A TEMPERATURE BELOW THAT AT WHICH THE SOLVENT IS SUBSTANTIALLY SOLUBLE IN WATER, SETTLING THE AQUEOUS MIXTURE THUS PRODUCED AT SUCH A TEMPERTURE TO OBTAIN STRATIFICATION THEREOF, RECYCLING THE UPPER SOLVENT AND AROMATIC-CONTAINING STRATUM TO A SOLVENT RECOVERY ZONE AND DISCARDING THE MATERIAL BELOW SAID UPPER STRATUM. 